KR100581648B1 - Exchange apparatus, manufacturing method and using method thereof - Google Patents

Abstract

An exchange apparatus consisting of hollow thermoplastic tubes melt-bonded into a thermoplastic material is disclosed. In a preferred embodiment, the hollow tube is formed by joining the tubes with the cord and then thermally annealing the cord to fix the vertices and bends of the joint. The cord provides an improved flow distribution of fluid around the hollow tube in the exchange device. The exchange device is chemically inert and cross-flow filtration is useful for heat and mass transfer in harsh chemical environments.

Exchanger, heat exchange, mass transfer, crossflow filtration, hollow tube, cord

Description

Exchange device, manufacturing method and its use {EXCHANGE APPARATUS, MANUFACTURING METHOD AND USING METHOD THEREOF}

This application is based on Provisional Patent Application No. 60 / 326,234, filed Oct. 1, 2001 under the name Fluid Exchange Device. This application is related to co-pending application as filed concurrently with this application as US Patent Application No. 60 / 326,357, filed Oct. 1, 2001, with Applicant's reference number 200100293 (formerly MYKP-621).

FIELD OF THE INVENTION The present invention relates to hollow tube or hollow fiber thin film exchange apparatus useful for the field of heat transfer, particle filtration, and mass transfer. The apparatus includes a housing that includes a hollow tube that is already plaited and heat annealed to melt-bond to secure the joint. The apparatus has a high packing density of hollow tubes with increased fluid flow distribution provided by the joined hollow tubes. The device provides a large contact area in a small volume without the need for a baffle. The device is made from a chemically inert thermoplastic material and has the ability to operate in organic liquids and corrosive and oxidizing liquids at high temperatures.

Hollow tubes and thin wall hollow tubes are commonly used in mass transfer, heat exchange, and cross flow particle filtration devices. In such applications, hollow tubes or fibers provide a high surface to volume ratio that allows for greater heat and mass transfer in smaller volumes than devices made of flat sheet materials of similar composition.

The hollow fiber or hollow tube comprises a porous or nonporous material between the outer diameter and the surface, the inner diameter and the surface, and the first and second surfaces or sides of the tube or fiber. The inner diameter defines the hollow portion of the fiber or tube and is used to hold one of the fluids. For the term tube side contact, the first fluid phase flows through a hollow, sometimes called a lumen, and remains separate from the second fluid phase surrounding the tube or fiber. In shell side contact, the first fluid phase surrounds the outer diameter and surface of the tube or fiber and the second fluid phase flows through the lumen. In an exchange apparatus, the packing density relates to the number of useful hollow fibers or hollow tubes that can be potted in the apparatus.

Examples of applications in semiconductor fabrication requiring heating of liquids are sulfuric acid and hydrogen peroxide photoresist stripping solutions, hot phosphoric acid, ammonium hydroxide and hydrogen peroxide SC1 cleaning solutions for etching silicon nitride and aluminum metal, hydrochloric acid and hydrogen peroxide SC2 cleaning solutions, hot deionized water Rinse, and heated organic amine-based photoresist stripper.

Post-use cooling in a bath of heated liquid, in particular a photoresist stripping solution, phosphoric acid, SC1 and SC2 washing solution, is necessary before discarding the used chemicals. Electrochemical plating baths and apparatus are sometimes maintained at temperatures below room temperature.

On a wafer processing track apparatus, accurate and repeatable control of the temperature of the liquid, such as the dielectric, photoresist, antireflective coating, and spin on the developer before dispensing onto the wafer, requires heating or cooling of this liquid.

The heat exchanger is a device that transfers heat from one fluid, a processing fluid, and a second working fluid. Polymer based heat exchangers are used to heat and cool chemicals for such applications because of their chemical inertness and resistance to corrosion. However, polymer heat exchange devices are usually large, because of the low thermal conductivity of the polymers used within the device, large heat transfer surface areas are required to achieve a given temperature change. Braiding of the tubes is used to prevent the tubes from being unevenly spaced when used in an open vessel heat exchanger. Such devices take up considerable space and require a large holding volume of chemical or exchange fluid and are expensive to make. Such devices also require fragile O-ring seals and are also ion and particle contamination sources.

Quartz heaters are also used to heat liquids used for semiconductor processing. Quartz is susceptible to fracture, and exposed resistively heated surfaces pose a fire and explosion hazard, especially for liquids that emit organic liquids and flammable gases.

Gas-to-liquid contactors or exchangers using hollow fiber tubes are used to remove or add gases from liquids in semiconductor manufacturing. Commercial gas to liquid contactors use baffles to improve mass transfer between fluids. Typical applications for contact thin film systems are to remove dissolved gases from the liquid (“degassing”) or to add gaseous substances to the liquid. For example, a wet bench is a wafer processing apparatus in which ozone gas is added to very pure water to contact the semiconductor wafer for cleaning and oxide growth.

Crossflow filtration is used to remove suspended solids, such as abrasive particles, used in chemical and mechanical polishing slurries in semiconductor manufacturing. Chemical, mechanical slurry streams contain, in addition to solid slurry materials, oxidants such as hydrogen peroxide in combination with acids and bases, such as hydrochloric acid or ammonium chloride. Chemical and mechanical polishing tools are examples of wafer processing apparatus used in semiconductor manufacturing.

To achieve cross flow filtration, mass transfer, and heat transfer using contactors made from hollow tubes or porous hollow fibers, baffles are commonly used to promote flow across tubular elements. Various designs for baffles for improving heat and material transfer to hollow tubes are detailed in the literature. U. S. Patent No. 5,352, 361 discloses a manner of baffling for hollow fiber gas to liquid contactors. Such baffles are useful for polyethylene-based hollow tubes in which methods for filling and rotating laminate baffles are readily practiced. Baffling of perfluorinated tubes is not practical when using this technique. US Pat. No. 4,749,031 discloses baffling with perfluorinated baffles in which individual hollow tubes are screwed. Manufacturing exchange contactors using this technique is cumbersome and expensive. U. S. Patent No. 4,360, 059 describes a spiral heat exchanger prepared from a casting material such as aluminum. Such a method does not consider the use of thermoplastic materials and does not address the need for substantially large surface areas required for thermoplastic materials with low thermal conductivity.

U. S. Patent No. 3,315, 740 discloses a method of joining tubes to each other by fusion for use in a heat exchanger. Tubes of thermoplastic material are collected in such a way that the ends of the tubes are in parallel contact. The ends of the collected tubes have a thermoplastic inner surface and are located in a sleeve that is rigid relative to the tubes. Fluid heated to a temperature at least corresponding to the softening point of the thermoplastic material is introduced into the end of the tube. A pressure difference is then imposed across the walls of the tubes such that the pressure in the tube is greater than the pressure on the outer surface of the tube, thereby causing the tubes to expand and fuse with the surface of the adjacent tube. Such a method creates a non-uniform pattern of entry into the hollow of the tube resulting in a non-uniform flow distribution over the tube. Such a method also requires a relatively thick walled tube to provide sufficient thermoplastic to form a seal with the housing sleeve. It is not contemplated to use such filling methods to form end structures or unitary end blocks, and to heat fix them prior to filling to braid the tubes to provide increased flow distribution.

Canadian Patent No. 1252082 discloses a way to make a spiral wound polymer heat exchanger. Such devices require mechanical fixtures to hold the tubes in place and thus require large volumes of space.

US Pat. No. 4,980,060 and US Pat. No. 5,066,379 describe melt bonded filling of porous hollow fiber tubes for filtration. Such invention does not disclose the conditions required to achieve melt bonding of nonporous thermoplastic tubes for the preparation of unitized end blocks for use in phase and heat exchange. Such an invention does not take into account the twisting or braiding of the hollow tubes and does not consider annealing the fibers prior to filling to achieve a structure on the immersed tube for increased flow distribution.

Alan Gableman and Hwang Sun-Tak describe the importance of uniform fiber spacing in the journal Membrane Science, Vol. 159 (1999), pages 61-106 to achieve better mass transfer within hollow tube contactors. The authors admit that hand-made modules have more uniform fiber spacing, but the cost of such modules does not justify their high manufacturing costs. Such an arrangement can be applied to hollow tube heat exchange and crossflow devices.

U. S. Patent No. 5,224, 522 describes a method and apparatus for making woven hollow fiber tapes for use in exchange devices such as blood oxygen dispensers and heat exchangers. Such apparatus and methods require expensive and complex weaving equipment to secure the fibers in a good relationship within the tube mat.

At present, due to the high cost and large size of the required equipment, it is impractical to use a thermoplastic heat exchanger for large heat loads, shell side liquid flow, or efficient shell side cross flow filtration. Metal heat exchangers are not allowed for use in semiconductor manufacturing because of the chemical nature of the chemicals and the need to remove metal and particulate impurities from the processing liquid. What is needed is a thermoplastic device for heat exchange, mass transfer, or crossflow filtration with large surface area, uniform fiber spacing, and minimal volume. The device should eliminate the need for baffles.

The present invention provides a device with a large surface area useful for mass transfer, heat exchange, or crossflow particle filtration. The apparatus consists of a thermoplastic material and comprises hollow thermoplastic fibers or hollow tubes melt-bonded into the thermoplastic to form a unified end block. Optionally, a device comprising a unified end block is melt bonded into a thermoplastic housing having fluid inlet and fluid outlet connections for processing and working fluids contacted across hollow fibers or hollow tubes. A method of making a device is provided and described. Methods of using the apparatus are also provided and described.

In one embodiment, the hollow tubes in the device are braided, coalesced or twisted together to form a cord of tubes or fibers before melt bonding into the thermoplastic to form a unified end block. Such cords provide an increased flow distribution of fluid through the device without the need for baffling. The high packing density of the hollow tube or cord is achieved by the present invention.

In another embodiment, a cord comprising a hollow tube or fiber is annealed in an oven to fix the shape of the twisting, coalescence, or braiding of the hollow tube or fiber in place prior to the melt bonding process. Alternatively, the hollow tube or cord may be wound around a rod, another hollow tube, or template, and the shape of the hollow tube or cord may be fixed by thermal annealing by the template. Braided or twisted cords can be wound on a rack and thermally annealed to fix the seam, geometry, and length of the cords. The braided or twisted cord is removed from the rack as a bundle of continuous cords and then melt bonded into the thermoplastic to form a unified end block. In other embodiments, the annealed cords can be unwound to provide individual non-circumferential hollow tubes or fibers. These individual hollow tubes are melt bonded into the thermoplastic wells as bundles. Optionally, the individual acyclic hollow tubes or fibers in the annealed cord or united end block are melt bonded to a thermoplastic housing having fluid inlet and fluid outlet connections for the processing and working fluids exchanged by the device.

1A to 1D are schematic diagrams showing examples of twisted and braided hollow tubes.

2A is a schematic diagram of a cross section of an exchange apparatus with an acyclic hollow tube fused into a thermoplastic resin.

FIG. 2B is a schematic illustration of a cross section of an exchange apparatus with an acyclic hollow tube fused into a thermoplastic resin having fluid inlet and outlet connections. FIG.

FIG. 2C is a schematic diagram of a cross section of an exchange apparatus with an acyclic hollow tube fused into a thermoplastic resin having a housing having a fluid inlet and a fluid inlet and outlet connection.

3 is a schematic view of a cross section of an exchange apparatus with twisted hollow tubes fused into a thermoplastic resin having a housing having a fluid inlet and a fluid inlet and outlet connection.

4 is a schematic view of a cross section of an exchange apparatus with braided hollow tubes fused into a thermoplastic resin having a housing with fluid inlet and outlet connections and fluid connections.

FIG. 5 is a schematic diagram illustrating an end view of an exchange apparatus having braided hollow tubes fused into a thermoplastic resin having a housing having a fluid inlet and a fluid inlet and outlet connection.

6 is a table detailing the performance of the heat exchanger described in Examples 2 and 3. FIG.

7 is a micrograph of an end of a hollow tube melt bonded into a thermoplastic using the method of the present invention.

8 is a table detailing the performance of the 20-tube heat exchanger described in Example 6. FIG.

9 is a table detailing the performance of the 680-tube heat exchanger described in Example 7. FIG.

The present invention relates to apparatus for heat and mass transfer operations and other phase separation applications. The invention also describes a method for making a unitary end block that is melt bonded to a device comprising a braided or twisted thermoplastic hollow tube or hollow fiber. Cords in the practice of the present invention are referred to as one or more fibers and / or tubes that are twisted, coalesced or braided together to form a unit that can be filled or fused by the method of the present invention into a well of thermoplastic. Melt bonding is performed by thermoplastic polymers. While the present invention will be described with respect to nonporous poly (tetrafluoroethylene-co-perfluoromethylvinylether) hollow tubes, the present invention will be described herein as various thermoplastic tubes and / or porous It should be understood that this can be accomplished using a thin film of fiber. In addition, while the present invention is described with respect to twisted pairs of poly (tetrafluoroethylene-co-perfluoromethylvinylether) hollow tubes, the present invention is twisted, woven, joined or braided to form what is referred to below as cords. It should be understood that various hollow tubes or hollow fibers can be made. Finally, while the present invention is described with respect to a device for heat exchange, similar devices using porous hollow tubes or hollow fibers can be made for use in the field of mass transfer and crossflow filtration.

For the purposes of the present invention, a single unwound annealed tube is considered an acyclic tube. Acyclic tubes are tubes that have a non-annular outer dimension that is continuous on a longitudinal axis that moves from one end of the tube to the other end. Examples include permanently twisted hollow circular tubes, triangular shaped tubes or fibers, square shaped tubes or fibers, or square shaped tubes or fibers, such as spiral coils, single unwound annealed fibers or extruded tubes under such conditions. Including but not limited to.

Braided, coalesced, twisted, or acyclic geometry of the hollow tube or fiber provides for increased flow distribution across and within the hollow tube. The device provides a large fluid contact area in a small volume without the need for a baffle. Single or unified end block structures of devices with chemically inert materials of the structure eliminate the need for o-rings and allow the use of device operation by various fluids at elevated temperatures.

Two or more hollow tubes may be joined, twisted, or braided with a cord by hand or by using commercially available winding and braiding equipment. In practicing the present invention, a plurality of hollow tubes may be woven together to form a mat of the hollow tubes. For the purposes of this specification and the appended claims, the terms mat and cord are used interchangeably. The twist of the tube per 305 mm (feet) in the cord is defined by the distance λ ₁ as shown in FIG. 1A. In Fig. 1A, two tubes are shown twisted together, but any number of tubes can be twisted together to form a cord. In FIG. 1A, the parameter λ ₁ describes the distance from the apex to the apex of the hollow tube 10 twisted with the hollow tube 12 or from the bend to the bend. The smaller value of the parameter λ, for example the parameter λ ₂ of FIG. 1B, accounts for a greater number of twists or bends between the hollow tubes 14, 16. Two or more hollow tubes may be braided together to form a cord. For braided hollow tubes as shown for individual tubes 18, 20, 22 in Fig. 1C, the dimensions of cord adhesion are described by the parameter λ ₃ . The individual hollow tubes 24, 26, 28 are more closely braided as shown in Fig. 1D, so that the parameter λ ₄ is smaller than λ ₃ . The value of λ can range from 1 per 305 mm (feet) to 50 per 305 mm (feet), preferably from 5 to 25 vertices or bends per 305 mm (feet). The number of hollow tubes twisted or braided to form a cord may range from 2 to 100, but more preferably 2 to 10 hollow tubes.

The invention is described in more detail with reference to FIG. 2A. As schematically shown in FIG. 2A, portions of each end of the individual thermoplastic acyclic tubes 36, 38, 40 are thermoplastic to form two single ends or a unified end block structure 32, 34. It is melt bonded with the resin in a fluid sealing manner. Any number of thermoplastic hollow tubes can be fused into the thermoplastic resin. FIG. 2B shows a cross section of the exchange device further comprising fluid connection ports 40, 42 coupled to unitary end blocks 34, 32 with end caps 44, 46. The end cap and fluid connector allow the first fluid to flow through the hollow tubes 36, 38, 40 from a source not shown. Two sides of a typical hollow tube or hollow fiber 38 of the present invention are further characterized by surfaces 37, 39. FIG. 2C shows a cross section of an exchange device further comprising a housing 52 coupled to united end blocks 32, 34 and having one or more fluid connector ports 48, 50.

In FIG. 3, an embodiment of the exchange device is shown to further comprise a cord of twisted hollow tube. The cord of this figure consists of hollow tubes 54, 56; 58, 60; 62, 64. A portion of the end of each cord is melt bonded to the thermoplastic in fluid sealing manner to form a unified end block 32, 34. The device may have an optional housing 52 and end caps 44 and 46 coupled to the united end block. In FIG. 3, at least one fluid flow distributor 66 may optionally be fitted, screwed or engaged into one or more of the housing fluid connection ports 48, 50.

In Figure 4, an embodiment of the exchange device is shown to further comprise a cord of braided hollow tubes. The cord of this figure consists of three or more hollow tubes braided together to form the cord shown by 70 and 72. The ends of each cord are melt bonded in a fluid sealing manner with the thermoplastic to form the unified end blocks 32, 34. The device may have an optional housing 52 and end caps 44 and 46 coupled to the united end block. In FIG. 4, at least one fluid flow distributor 66 may optionally be fitted, screwed or engaged within one or more of the housing fluid connection ports 48, 50. An end view of the exchange device shown in FIG. 4 is schematically shown in FIG.

Referring to Fig. 3, the operation of one embodiment of the present invention which is a heat exchanger will be described. The first fluid enters the exchange device through the fluid connection port 42 and enters the hollow tube at the opening 61 in the united end block 32. Fluid flows through the interior or lumen of the hollow tube and exits the tube through the unified end block 34 at the outlet opening 63. The first fluid exits the exchange device through the fluid connection port 40. The second fluid enters the exchange device through the housing fluid port 48 and optional flow distributor 66. The first fluid is separated from the second fluid by two surfaces and walls of the hollow tube. The second fluid enters the housing through the connection 48 and substantially fills the space between the inner wall of the housing and the outer diameter of the fiber. Energy is transferred between the first and second fluids through the thermoplastic hollow tube wall. The second fluid exits the housing through the fluid connector port 50. Examples of fluids include liquids, vapors of liquids, gases, and supercritical fluids.

Manufacturers manufacture thin films from a variety of materials, the most common of which are synthetic polymers. An important grade of synthetic polymers is thermoplastic polymers that can flow and shape when heated and restore their original solid properties when cooled. As the application conditions under which tubes or thin films are being used become more stringent, the materials that can be used are limited. For example, organic solvent-based solutions used for water coating in the microelectronics industry will dissolve or swell and weaken some polymer tubes and thin films. Hot stripping baths in the same industry consist of strong acidic and oxidizing compounds that break down thin films and tubes made of ordinary polymers.

Outer diameters ranging from 0.178 to 12.7 mm (0.007 to 0.5 inch), more preferably 0.635 to 2.54 mm (0.025 to 0.1 inch) diameter, 0.0254 to 0.254 mm (0.001 to 0.1 inch), preferably 0.0762 to 1.27 mm ( Hollow tubes made from thermoplastics with wall thicknesses ranging from 0.003 to 0.05 inches) thickness are useful in practicing the present invention. The tubes can be used individually or the tubes can be combined by braiding, coalescing or twisting to form a cord consisting of multiple hollow tubes.

및 FEP 테프론

열가소성 수지는 델라웨어주 윌밍톤의 듀폰(DuPont)에 의해 제조된다. 네오프론

PFA는 다이킨 인더스트리즈(Daikin Industries)로부터 구입 가능한 중합체이다. MFA 하프론

은 뉴저지주 쏘로페어의 오시몬트 유에스에이 인크.(Ausimont USA Inc.)로부터 구입 가능한 중합체이다. 예비 성형된 MFA 하프론

및 FEP 테프론

튜브는 사우쓰 캐롤라이나주 오랜지베리의 제우스 인더스트리얼 프로덕츠 인크.(Zeus Industrial Products Inc.)로부터 구입 가능하다. 본 발명을 실시하는 데 있어서 유용한 다른 열가소성 수지 또는 이의 혼합물은 폴리(클로로트리플루오로에틸렌 비닐리덴 플루오라이드), 폴리비닐클로라이드, 폴리프로필렌과 같은 폴리올레핀, 폴레에틸렌, 폴리메틸펜텐, 초고분자량 폴레에틸렌, 폴리아마이드, 폴리술폰, 폴리에테르에테르케톤, 및 폴리카보네이트를 포함하지만 그에 제한되지 않는다.Examples of perfluorinated thermoplastic resins or mixtures thereof useful in practicing the present invention are polytetrafluoroethylene-co-perfluoromethylvinylether (MFA), polytetrafluoroethylene-co-perfluoropropyl Vinyl ether (PFA), polytetrafluoroethylene-co-hexafluoropropylene (FEP), polyvinylidene fluoride (PVDF). PFA Teflon

And FEP Teflon

Thermoplastics are manufactured by DuPont, Wilmington, Delaware. Neoprene

PFA is a polymer available from Daikin Industries. MFA Halfron

Is a polymer available from Ausimont USA Inc. of Sorfair, NJ. Preformed MFA Halflon

And FEP Teflon

The tube is available from Zeus Industrial Products Inc. of Orangeberry, South Carolina. Other thermoplastic resins or mixtures thereof useful in practicing the present invention include poly (chlorotrifluoroethylene vinylidene fluoride), polyvinylchloride, polyolefins such as polypropylene, polyethylene, polymethylpentene, ultra high molecular weight polyethylene, Polyamides, polysulfones, polyetheretherketones, and polycarbonates.

The hollow thermoplastic tube can be impregnated with a thermally conductive powder or fiber to increase its thermal conductivity. Examples of useful thermally conductive materials include, but are not limited to, glass fibers, metal nitride fibers, silicon and metal carbide fibers, or graphite. The thermal conductivity of the hollow thermoplastic tubes or impregnated thermoplastic hollow tubes useful in the present invention is greater than 0.05 W / m / ° K.

Hollow tubes useful in practicing the present invention in the field of particle filtration and mass transfer such as gas contact, liquid degassing, and overevaporation include hollow fiber membranes. Suitable thin films include hollow fibers made from polytetrafluoroethylene-co-perfluoropropylvinylether (PFA) or ultra high molecular weight polyethylene available from Mykrolis Corporation, Billerica, Massachusetts.

In a preferred embodiment, the twisted, coalesced or braided tube forms a continuous cord. The cord can be wound around a rectangular metal frame as described in WO 00/44479, with the distance between the parallel sides defining the length of the exchange device. The cord wound on the metal frame is placed in the oven below the melting point of the hollow tube. The tube is thermally annealed at a temperature below its melting point and then cooled to fix the vertices and curves in the braided, coalesced, or twisted tube. Annealing of the cord tube takes place for 15 to 60 minutes, more preferably for 30 minutes, below the melting point which is usually below 250 ° C, more preferably 100 to 200 ° C. In other embodiments, the twisted, coalesced or braided tube may be annealed on the spool.

In another embodiment, the braided or twisted tubes can be thermally annealed in a first step, and then the individual tubes are separated from each other after cooling to form a single tube of self-supporting spiral or acyclic shape. Thermal annealing fixes the vertices and bends of the hollow tubes so that individual hollow tubes or cords can be separated and processed without being straightened.

In one embodiment of the invention, the thermally annealed and fixed cords of the hollow tubes may be connected by the method described in US Pat. No. 3,315,750, which is incorporated herein by reference in its entirety. The cords can also be connected to each other and to the housing by the injection molding method described in European Patent Application No. 0 559 149 A1, which is incorporated herein by reference in its entirety. In a preferred embodiment, the methods described in US Patent Application Nos. 60 / 117,853 and WO 00/44479, filed Jan. 29, 1999, which are incorporated herein by reference in their entirety, are useful in practicing the present invention.

In the practice of the present invention the term unitary end block or unitary end structure is used to describe the mass or well of a thermoplastic resin to which one or more hollow tubes or cords are bonded or melt bonded. 7 shows examples of hollow tubes melt-bonded to a thermoplastic resin and hollow tubes not melt-bonded to a thermoplastic resin to form a unified end block structure. US patent application 60 / 117,853 describes hollow fibers bonded to thermoplastic resins. Optionally, a thermoplastic end cap or thermoplastic housing having a fluid connector port can be melt bonded to one or more of the unitized end blocks. For purposes of illustrating the present invention, a unified end block comprising a hollow tube, a thermoplastic resin, and a thermoplastic housing is described. A housing forming a monolith consisting solely of perfluorinated thermoplastic material is prepared by first pretreating the surfaces of both ends of the housing prior to the filling and joining step. A unified end block end structure, which means that the braided or twisted tubes and fills are joined to the housing to form a monolith consisting only of perfluorinated thermoplastic material, is prepared by first pretreating the surfaces of both ends of the housing prior to the filling and joining step. . This is done by melt bonding the filler material to the housing. The inner surface of both ends of the housing is heated to or close to its melting point and is a powder of polytetrafluoroethylene-co-perfluoromethylvinylether thermoplastic filler resin available from Oscillmont USA Inc. of Sorfair, NJ. It is immediately immersed into the cup containing it. Since the surface temperature of the housing is higher than the melting point of the filling resin, the filling resin is fused to the thermoplastic housing. The housing is then taken out and polished with a hot air blower to melt any excess unmelted thermoplastic powder. It is preferred that each end of the tube is treated at least twice by this pretreatment.

PFA 또는 MFA 쉘 튜브 내로 삽입된다. 쉘 튜브는 선택적으로 입구 및 출구 포트를 형성하도록 그의 표면에 용융 결합된 유체 피팅을 갖는다. 쉘 튜브 내의 튜브 코드의 패킹 밀도는 3 내지 99 체적%, 더욱 양호하게는 20 내지 60 체적%의 범위 내에 있어야 한다.Annealed and twisted hollow tube cords are poly (tetrafluoroethylene-co-perfluoro (alkyvinylether)), Teflon

It is inserted into a PFA or MFA shell tube. The shell tube optionally has a fluid fitting melt-bonded to its surface to form inlet and outlet ports. The packing density of the tube cords in the shell tube should be in the range of 3 to 99 volume percent, more preferably 20 to 60 volume percent.

MFA 940 AX 수지이다. 방법은 적어도 하나의 폐쇄 단부를 구비한 어닐링되고 꼬인 중공 튜브 코드 길이의 다발의 일부를 용기 내에 유지되는 용융된 열가소성 중합체의 풀(pool) 내에 만들어진 임시 리세스 내로 수직으로 위치시키는 단계를 포함한다. 중공 튜브는 한정된 수직 위치 내에 유지되어, 열가소성 중합체가 임시 리세스 내로 중공 튜브 둘레로 그리고 섬유를 따라 위로 유동하여 섬유들 사이의 사이공간을 완전히 충전하도록 열가소성 중합체를 용융 상태로 유지한다. 임시 리세스는 중공 튜브 다발을 제 위치에 위치 및 고정시키기에 충분한 시간 동안 용융된 충진 재료 내의 리세스로서 유지되는 리세스이며, 그 다음 용융된 열가소성 수지에 의해 채워질 것이다. 리세스의 임시적인 특성은 충진 재료가 유지되는 온도, 충진 재료가 중공 튜브 다발 배치 중에 유지되는 온도, 및 충진 재료의 물리적인 특성에 의해 제어될 수 있다. 중공 튜브의 단부는 밀봉 또는 플러깅에 의해, 또는 양호한 실시예에서는 루프로 형성됨으로써 폐쇄될 수 있다.Filling and joining of the tube cord into the housing can be done in one step. Preferred thermoplastic filler materials are Hypron, available from Oscillmont USA Inc., Soropair, NJ.

MFA 940 AX resin. The method includes vertically placing a portion of the bundle of annealed and twisted hollow tube cord lengths having at least one closed end into a temporary recess made in a pool of molten thermoplastic polymer held in the container. The hollow tube is held in a defined vertical position to keep the thermoplastic polymer in a molten state so that the thermoplastic polymer flows up into the temporary recess around the hollow tube and along the fiber to completely fill the interspace between the fibers. The temporary recess is a recess that is maintained as a recess in the molten filler material for a time sufficient to position and fix the hollow tube bundle in place and will then be filled by the molten thermoplastic. The temporary nature of the recess can be controlled by the temperature at which the fill material is maintained, the temperature at which the fill material is maintained during the hollow tube bundle placement, and the physical properties of the fill material. The end of the hollow tube can be closed by sealing or plugging, or in a preferred embodiment by forming into a loop.

Once the first end of the device is filled and fused into a unified end block comprising a hollow tube, a housing, and a thermoplastic resin, the second end of the device is filled. The process allows the filled resin to become transparent and trapped in the heating cup by an external heating block or other heat source at a temperature in the range of about 265 ° C to about 285 ° C, preferably in the range of about 270 ° C to about 280 ° C. Heating until it disappears. The rod is inserted into the melt to create a recess or cavity. The housing and the hollow tube bundle are then inserted into the cavity. It is important to know at this point that the hollow tube bundles and the housing are not in contact with the filling resin. The molten resin flows over a period of time by gravity to fill the gap, and at the same time fills the hollow tube and bonds it to the housing. The filled end is cut after cooling and the lumen of the hollow tube is exposed. The filled surface is then polished using a hot air blower to melt away the damaged or roughly filled surface. For modules with more than 2000 hollow tubes, the module may have filling defects that can be repaired using clean solder iron to melt and close damaged areas.

Another embodiment of the invention is useful for filling spiral cords composed of hollow tubes. Each end of the twisted or braided hollow tube is filled in a metal mold in a first step. The mold is slightly smaller than the inner diameter of the shell tube and can be made from aluminum or nickel or a similar alloy. After filling and cooling, the mold is removed. The end of the hollow tube in the unified end block is opened by cutting as described above. After both ends of the hollow tube are filled, the formed unified end block structure is inserted into a pre-heated MFA or PFA shell housing tube or end cap, and the unified end block is fused to the housing tube or end cap in a short heating process. .

In the preferred embodiment of the present invention shown in Figure 3, at least one thermoplastic tube 66 is inserted into at least one of the fluid fittings 48 on the shell side of the exchange device. Preferably, the tube is positioned into the portion of the tube bundle closest to the fitting. The tube may be thermally coupled to the housing or fitted into the shell fitting. The tube provides improved flow distribution of the fluid within the device.

, 필라

, 스와게로크

, VCO

, 표준 파이프 나사 피팅, 또는 바브 피팅을 포함하지만 그에 제한되지 않는다. 양호한 실시예에서, 두 개의 유체 연결부가 처리 유체에 대해 제공되고, 하나는 장치 내로의 유체의 유동을 위한 입구 연결부이고, 하나는 장치로부터의 유체의 유동을 위한 출구 연결부이다. 처리 유체는 튜브를 통해서 또는 튜브의 외부를 가로질러 유동할 수 있다. 처리 유체를 위한 입구 및 출구 연결부는 용접, 나사 결합, 플랜징, 또는 열가소성 수지에 대한 용융 결합에 의해 단일화된 말단부 블록에 결합될 수 있다. 하우징이 교환 장치에 대해 제공되면, 처리 유체를 위한 입구 연결부는 하우징 및/또는 단일화된 말단부 블록에 용접, 나사 결합, 또는 플랜징에 의해 결합될 수 있다. 양호한 실시예에서, 연결부는 하우징 및/또는 단일화된 말단부 블록에 용융 결합된다. 하나 이상의 유체 연결부가 하우징을 통한 작업 유체의 유동 또는 하우징으로부터의 여과된 액체의 유동을 위해 제공될 수 있다. 하우징을 통한 작업 유체 또는 여과된 액체의 유동을 위한 하나 이상의 연결부는 용접, 나사 결합, 또는 플랜징에 의해 하우징에 결합될 수 있다. 양호한 실시예에서, 연결부는 하우징에 용융 결합된다.Fluid fittings useful for connecting the device of the present invention to a source of working and processing fluids are Flaretech

, Pillar

, Swagerok

, VCO

Include, but are not limited to, standard pipe threaded fittings, or barb fittings. In a preferred embodiment, two fluid connections are provided for the processing fluid, one is an inlet connection for the flow of fluid into the device and one is an outlet connection for the flow of fluid from the device. The processing fluid may flow through the tube or across the outside of the tube. Inlet and outlet connections for the processing fluid can be joined to the unified end block by welding, screwing, flanging, or melt bonding to the thermoplastic. Once the housing is provided for the exchange device, the inlet connection for the processing fluid can be joined by welding, screwing, or flanging to the housing and / or the unified end block. In a preferred embodiment, the connection is melt bonded to the housing and / or the unified end block. One or more fluid connections may be provided for the flow of working fluid through the housing or the flow of filtered liquid from the housing. One or more connections for the flow of working fluid or filtered liquid through the housing may be coupled to the housing by welding, screwing, or flanging. In a preferred embodiment, the connection is melt bonded to the housing.

General procedure

유체 피팅이 PFA 튜브의 각각의 단부로부터 대략 50.8 mm(2 인치)에 결합되었다. 장치의 각각의 단부는 뉴저지주 쏘로페어의 오시몬트 유에스에이 인크.로부터 구입한 하이프론

MFA 940 AX 수지를 사용하여 약 40시간 동안 275℃에서 충진되었다. 40시간 충진 후에 각각의 단부의 냉각은 150℃까지 0.2℃/min의 속도로 제어되었다. 단일화된 말단 블록 단부는 수지가 제거되었고 중공 튜브는 선반 또는 나이프를 사용하여 충진된 장치의 단부를 가공함으로써 개방되었다. 충진된 교환기를 위한 유체 피팅은 튜브의 각각의 단부 상에 파이프 나사를 새김으로써 또는 튜브 상으로 단부 캡을 열 융합시킴으로써 만들어졌다.Preformed hollow MFA tubes with a 1.19 mm (0.047 inch) inner diameter and 0.152 mm (0.006 inch) wall thickness were purchased from Zeus Industrial Products Inc., Orangeberry, South Carolina. Cords for filling were made by hand twisting these pairs of hollow MFA tubes to obtain about 12 revolutions per 305 mm (feet) of cord. A single cord was wound around a metal frame 203 mm (8 inches) wide and 457 to 686 mm (18 to 27 inches) long and it was possible to make about 75 turns of cord on the metal frame. The frame and wound cords were annealed at 150 ° C. for 30 minutes in an oven. About 75 loops of cord, measured from 457 to 686 mm (18 to 27 inches) each, were obtained from the rack after annealing. Cords from a single rack or multiple racks were collected and placed into a PFA tube, pre-heated and MFA coated length measured from 406 to 635 mm (16 to 25 inches). The inner diameter of the tube was 25.4 to 57.2 mm (1 to 2.25 inches) and ¼ "Flaretech

The fluid fitting was joined approximately 50.8 mm (2 inches) from each end of the PFA tube. Each end of the device is a hypron purchased from Osmont U.S. Inc., Sorofair, NJ.

Filled at 275 ° C. for about 40 hours using MFA 940 AX resin. After 40 hours of filling the cooling at each end was controlled at a rate of 0.2 ° C./min to 150 ° C. The unified end block end was removed from the resin and the hollow tube was opened by machining the end of the filled device using a lathe or knife. Fluid fittings for filled exchangers were made by engraving pipe screws on each end of the tube or by heat fusion of the end cap onto the tube.

Example 1

A prototype heat exchanger with a housing with a PFA tube of 25.4 mm (1 inch) inner diameter was prepared by Procedure 1 except that the tube was not twisted or annealed. The device included 150 tubes of straight MFA tubes measured 381 mm (15 inches) in length.

The prototype was tested under the following conditions. Hot water at a temperature of 63 ° C. was fed into the tube side of the device at a flow rate of approximately 1750 ml / min. Cold water at 19 ° C. temperature was fed into the shell side of the device at a flow rate of approximately 1070 ml / min. The hot and cold passages flowed countercurrent to each other. Inlet and outlet temperatures and flow rates were recorded every 5 minutes for the tube and shell side fluid streams for 1 hour. The results from this experiment are detailed in Table 1 shown in FIG. Under these conditions, the cold water was heated from 18.9 ° C. to 38.8 ° C. and a total of 1486 watts of energy was exchanged between the two fluids.

Example 2

Procedure 1 except that the prototype heat exchanger with a housing with a 25.4 mm (1 inch) inner diameter PFA tube includes about 150 hollow MFA tubes twisted together at about 12 twists per 305 mm (feet). Was prepared by. The twisted cord was annealed on a metal rack to yield approximately 75 cords measured about 381 mm (15 inches) in length.

The prototype was tested under the following conditions. Hot water at a temperature of 55 ° C. was supplied into the tube side of the device at a flow rate of approximately 1650 ml / min. Cold water at 19 ° C. temperature was fed into the shell side of the device at a flow rate of approximately 1070 ml / min. The hot and cold passages flowed countercurrent to each other. Inlet and outlet temperatures and flow rates were recorded every 5 minutes for the tube and shell side fluid streams for 1 hour. The results from this experiment are detailed in Table 1 shown in FIG. Under these conditions, the cold water was heated from 18.9 ° C. to 44.0 ° C. and a total of 1874 watts of energy was exchanged between the two fluids.

Example 3

This example shows how a wafer processing tool including the exchange apparatus of the present invention can be used to heat a liquid used to clean a semiconductor wafer.

An exchange device having 325 pairs of about 650 twisted hollow MFA tubes can be thermally annealed using the method of Procedure 1 to melt bond within a 50.8 mm (2 inch) inner diameter PFA tube. The length of the device is about 457 mm (18 inches) and has a volume of liquid of about 300 ml. The apparatus is part of a wafer processing tool and is connected in series to a source of a 10% aqueous hydrochloric acid solution containing about 1 volume percent hydrogen peroxide at its inlet fluid connection. The outlet of the exchange device is connected to a valve, an optional non-return valve, and a nozzle for dispensing the aqueous acid solution onto the substrate to be cleaned. One of the fluid inlet connections on the shell side of the exchange device is connected in series to the hot water source. Hot deionized water is commonly used at temperatures of about 75 ° C. in semiconductor plants. The heated water passing through the shell side of the exchanger heats the acid solution contained in the tube of the exchanger. After a variable time without fluid flow, the valve at the exit of the exchange device is opened so that the heated acid aqueous solution and oxidant are dispensed onto the wafer and used to clean the wafer. The valve is closed and the acid solution and oxidant flow into the hollow tube of the exchanger and are heated for the next distribution.

Example 4

This example shows how an exchanger for cross flow filtration can be made using a thermally annealed and coalesced porous hollow PFA tube.

The prototype filtration device with a housing with a 25.4 mm (1 inch) diameter PFA tube is a non-porous hollow MFA tube with 150 hollow porous PFA fibers having an outer diameter of 550 microns, available from Microlith Corporation, Billerica, Massachusetts. Prepared by Procedure 1, except for replacing. Hollow fibers can be spliced three times per strand and wound on a rack measured 381 mm (15 inches) in length. The joined and wound hollow fibers may be heat annealed at about 150 ° C. to fix the union and length of the hollow fibers. Heat annealed and coalesced hollow fibers are assembled into the device according to the method disclosed in WO 00/44479.

Housings for such devices include inlet and outlet port connections for the flow of fluids containing insoluble suspended materials such as colloids, gels, or solid particles. Examples of fluids containing suspended solid particles include alumina in chemical, mechanical polishing slurries, and examples of colloids in fluids may include silica. The fluid containing insoluble suspension material flows through the interior of the porous hollow fiber tube. The housing has a single fluid flow port connection for the flow of filtered liquid from the housing. Some of the liquid containing suspended solids flows across the coalesced porous hollow tube, some of the solids are retained by the porous membrane and some of the filtered liquid flows out of the fluid port on the housing through the membrane.

Example 5

This example shows how an exchange device for mass transfer of gas into a liquid can be made using a thermally annealed and coalesced porous hollow PFA tube.

The prototype filtration device with a housing with a 25.4 mm (1 inch) diameter PFA tube consists of 150 hollow MFA tubes with 150 hollow porous PFA fibers with an outer diameter of 550 microns, available from Microlith Corporation, Billerica, Massachusetts. It may be prepared by Procedure 1, except for replacing. Hollow fibers can be spliced three times per strand and wound on a rack measured 381 mm (15 inches) in length. The joined and wound hollow fibers may be heat annealed at about 150 ° C. to fix the length and length of the joints of the tubes. The heat annealed and coalesced hollow fibers can be assembled into the device according to the method disclosed in WO 00/44479.

The housing for such a device may have inlet and outlet port connections for the flow of deionized water through the interior of the porous hollow fiber tube. One of the two ports of the housing can be used to connect to a source of ozone gas generated by an ozone generator, for example, the Astex 8400 ozone generator available from Astex, Woburn, Massachusetts. Ozone gas is dissolved in water by permeation through a porous, coalesced hollow PFA tube. Excess ozone gas is exhausted through the second port of the housing. The water exiting the inside of the tube contains ozone gas dissolved in the water. This ozone water is useful for cleaning wafers using a modified RCA cleaning process.

Example 6

This example describes the heat exchange device of the present invention with 20 thin wall hollow PFA tubes. The apparatus was used to heat the flowing water in series.

PFA tubes of 432 mm (17 inches) long and 12.7 mm (0.5 inches) outer diameter were used as housing conduits. The housing conduit had inlet and outlet ports. The housing conduit was melt bonded to 26 1.05 mm inner diameter PFA tubes having a wall thickness of 0.15 mm at each end using PFA filled material. Two J-type thermocouples were placed in separate flow through the housing. One thermocouple was connected to the inlet port of the exchanger housing conduit and the second thermocouple was connected to the outlet port of the heater device housing conduit. In operation, treated water flows through the inlet thermocouple housing into the exchanger device housing and through the hollow tube. The working or exchange fluid flowed through the inlet thermocouple housing in a countercurrent manner into the shell side of the housing to contact the outside of the hollow tube. The exchange or working fluid then passes through the outlet port on the shell side of the housing conduit and the second outlet thermocouple housing. The treated water flowing through the exchanger tube exits the tube through the second outlet thermocouple housing. At a flow rate of 1000 ml per minute of water at a temperature of about 16 ° C. flowing into the shell side of the device, water flowing into the tube at a flow rate of 260 ml per minute at a temperature of 55.5 ° C. was cooled to 33.1 ° C. as it exited the tube. The performance of this device at different tube side flow rates is summarized in FIG.

Example 7

This example describes the heat exchange device of the present invention with 680 thin wall hollow MFA tubes. The apparatus was used to cool the flowing water in series.

이었고, 이들은 686 mm(27 인치) 이격되었으며 장치의 단부로부터 63.5 mm(2.5 인치)였다. 튜브 측면 유동을 위한 하우징 유체 피팅은 ¾" 플레어텍

이었고 하우징 튜브에 용융 결합되었다.Prototype heat exchanger with a PFA housing with a 57.2 mm (2.25 inch) inner diameter and 813 mm (32 inch) length includes about 680 hollow MFA tubes twisted together with about 12 twists per 305 mm (feet) Prepared by Procedure 1, except. The twisted cord was annealed on a metal rack to yield a cord measuring approximately 864 mm (34 inches) in length. Inlet fluid fittings on housing shell side ½ "Flaretech

And 686 mm (27 inches) apart and 63.5 mm (2.5 inches) from the end of the device. Housing fluid fitting for tube side flow is ¾ "Flaretech

And melt bonded to the housing tube.

The prototype was tested under the following conditions. Hot water at a temperature of 70.1 ° C. was fed into the tube side of the device at a flow rate of approximately 4.4 liters per minute. Cold water at a temperature of 14.5 ° C. was fed into the shell side of the device at a flow rate of approximately 6.6 liters per minute. The hot and cold passages flowed countercurrent to each other. Inlet and outlet temperatures and flow rates were recorded using an Agilent data register. The results from this experiment are detailed in the table of FIG. Under these conditions, the hot water in the tube was cooled from 70.1 ° C. to 22.9 ° C. and a total of 14,400 watts of energy was exchanged between the two fluids. The performance of this device at different flow rates is summarized in FIG.

Claims (26)

Exchange device, A plurality of thermoplastic hollow tubes having a structure selected from the group consisting of cords and acyclic tubes, each having two ends and hollows passing between them, At least one of the ends of the hollow tube is melt bonded through a thermoplastic at least at its periphery to form a united end block, and within the united end block the ends of the hollow tube are fused together by thermoplastics Coupled in a fluid seal, The unified end block has a through hole communication with the hollow portion of the unbonded portion of the tube, The unified end block has a first fluid inlet connection for supplying a first fluid to the hollow tube, a first fluid outlet connection for removing the first fluid from the hollow tube, Further comprising a housing melt-bonded to at least one of said united end blocks comprising said hollow tube, And the housing has at least one connection port for delivering a second fluid through the housing. The apparatus of claim 1, wherein the thermoplastic hollow tubes are twisted together. The apparatus of claim 1, wherein the thermoplastic hollow tube is joined with a cord. The apparatus of claim 1, wherein the thermoplastic hollow tube is joined with a cord and the cord is thermally annealed to secure the joint. The method of claim 1, wherein the hollow tube is polytetrafluoroethylene-co-perfluoromethylvinylether, polytetrafluoroethylene-co-perfluoropropylvinylether, polytetrafluoroethylene-co-hexafluoro A device composed of a thermoplastic resin or mixture thereof selected from the group consisting of ropropylene, polypropylene, polymethylpentene, and ultra high molecular weight polyethylene. The apparatus of claim 1, wherein the thermoplastic hollow tube is porous. The apparatus of claim 1, wherein the thermoplastic tube is impregnated with a thermally conductive material. It is a manufacturing method of the exchange apparatus, Forming a bundle comprising a plurality of thermoplastic hollow tubes having a structure selected from the group consisting of cords and acyclic tubes, each having two ends and hollows passing therebetween; Fusing the first end of the at least one bundle of thermoplastic hollow tubes with the thermoplastic resin to form a first unified end block, Fusing the second end of the at least one bundle of thermoplastic hollow tubes with the thermoplastic resin to form a second unified end block; Opening the tube ends of the first and second unified end blocks to provide fluid flow through the hollow tube fused with the thermoplastic resin, The tube is polytetrafluoroethylene-co-perfluoromethylvinylether, polytetrafluoroethylene-co-perfluoropropylvinylether, polytetrafluoroethylene-co-hexafluoropropylene, polypropylene, poly And a thermoplastic resin selected from the group consisting of methylpentene, and ultra high molecular weight polyethylene, or mixtures thereof. The method of claim 8, wherein the open end of the hollow tube fused to the thermoplastic resin has a cross section that is generally the same as the unbonded portion of the hollow tube. The method of claim 8, further comprising annealing the cord below the melting point of the thermoplastic hollow tube to secure the curve of the tube in the cord. The method of claim 10, wherein the annealed cord is separated into individual thermoplastic hollow tubes and then combined with the thermoplastic resin as a bundle of acyclic hollow tubes. 10. The method of claim 8, further comprising coupling at least one fluid connection port to the unified end block. 13. The method of claim 12 further comprising coupling a thermoplastic housing to the second united end block. A method of using the exchange device of claim 1 for heat transfer from a first fluid to a second fluid, Flowing a first fluid on the first side of the hollow tube; Flowing a second fluid on the second side of the hollow tube; Transferring energy between the first and second fluids through a wall of a thermoplastic hollow tube. The method of claim 14, wherein the fluid is a photoresist, antireflective coating, resist stripper, or photoresist developer. The method of claim 14, wherein the fluid is spin on a dielectric. The method of claim 14, wherein the fluid is a fluid containing copper ions. The method of claim 14, wherein the fluid is selected from the group consisting of acids, bases, oxidants, and mixtures thereof. The method of claim 14, wherein the liquid is an organic liquid. The method of claim 10, wherein the second fluid is selected from the group consisting of inert gas, water, polyethylene glycol compound, and vapor. The method of claim 14, wherein the first fluid is a gas. A method of using the exchange device of claim 6 for cross flow filtration of a fluid, Flowing a first fluid containing an insoluble suspending material on the first side of the hollow porous tube, Filtering a portion of the first fluid through the hollow porous tube, Wherein said hollow porous tube retains a portion of insoluble suspension material and wherein said portion of fluid passes through the hollow porous tube. A method of using the exchange device of claim 6 for mass transfer between fluids, Flowing a first fluid on the first side of the hollow porous tube; Flowing a second fluid on the second side of the hollow porous tube; Dissolving a portion of the second fluid into the first fluid. The method of claim 23, wherein the first fluid is an aqueous solution and the second fluid is a gas. Exchange device adapted to be connected in series with a fluid flow circuit, A housing with fluid fittings, A tube bundle comprising a plurality of acyclic tubes located within the housing and made from a thermoplastic resin, The tubes are arranged longitudinally and have two ends melt-bonded through a thermoplastic at the periphery to form a unitary end block, within which the ends of the acyclic tube are in fluid communication therethrough. Fluid sealingly coupled in a fused manner to allow, The housing includes a first fluid inlet for supplying a first fluid to the first end of the tube bundle to be in contact with a second fluid and a first fluid outlet connection for removing the contacted first fluid from the acyclic tube. Wherein the housing is configured to remove the second fluid in contact with a first fluid inlet connection for supplying a second fluid in contact with the first fluid to the volume formed between the inner wall of the housing and the acyclic tube. Device having a second outlet connection for. Fixing the thermoplastic hollow tube for the twisted, coalesced or braided exchange device around the frame, Annealing the hollow tube around the frame below its melting point such that the hollow tube is acyclic.

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